Siloxy substituted cocatalyst activators for olefin polymerization

Abstract

This description addresses ionic compositions of matter comprising positively charged cations [Ct] + and negatively charged anions [A] − , said anion comprising a central core Group 13 element to which are bound fluoroaryl ligands, at least one of said fluoroaryl ligands being substituted with a siloxy group represented by the symbols—SiOR 3 , wherein R is a C 1 -C 30 hydrocarbyl or hydrocarbylsilyl substituent. [Ct] + may be selected from any capable of use with olefin polymerization catalysts and typically will be from the group consisting of anilinium and ammonium cations, trityl carbenium cations, Group 11 metal cations, silylium cations, the cations of the hydrated salts of Group 1 or 2 metals, and derivatives of the foregoing anilinium, ammonium, trityl carbenium, and silylium cations containing C 1 -C 20 hydrocarbyl, hydrocarbylsilyl, or hydrocarbylamine substituents for one or more hydrogen atoms of said cations. The ionic compositions described can be used to activate olefin polymerization catalysts, and can be prepared so as to be soluble in aliphatic solvents. Syntheses and polymerization are illustrated.

I claim:  
     
       1. An ionic composition of matter comprising a positively charged cation [Ct] +  and a negatively charged anion [A] − , said anion comprising a central core Group 13 element to which are bound fluoroaryl ligands, at least one of said fluoroaryl ligands being substituted in the para-position with a siloxy group represented by the symbols —OSiR 3 , wherein each R is independently a C 1 -C 30  hydrocarbyl or hydrocarbylsilyl substituent. 
     
     
       2. The ionic composition of matter of  claim 1  represented by the formula: 
       
         
           [Ct] + [M(ArF) n ((ArF)OSiR 3 ) 4−n ] − ,  
         
       
       where [Ct] +  is cation capable of abstracting an alkyl group, or breaking a carbon-metal bond, from organometallic compounds containing such, M is boron or aluminum, ArF is a fluorinated aryl group, each R is a C 1 -C 20  hydrocarbyl or hydrocarbylsilyl substituent attached to the Si atom through a secondary or tertiary carbon atom, and n is 0-3. 
     
     
       3. The composition according to  claim 2  where [Ct] +  is selected from the group consisting of anilinium and ammonium cations, trityl carbenium cations, Group 12 metal cations, silylium cations, the cations of the hydrated salts of Group 1 or 2 metals, and derivatives of the foregoing anilinium, ammonium, trityl carbenium, and silylium cations containing C 1 -C 20  hydrocarbyl, hydrocarbylsilyl, or hydrocarbylamine substituents for one or more hydrogen atoms of said cations. 
     
     
       4. The composition of  claim 3  wherein ArF is a fluorinated or perfluorinated aryl group wherein said aryl group is selected from the group consisting of phenyl, biphenyl, and napthyl. 
     
     
       5. The composition of  claim 4  wherein each R is a C 1 -C 10  a linear, branched or cyclic aliphatic hydrocarbyl or hydrocarbylsilyl substituent. 
     
     
       6. The composition of  claim 5  wherein at least one R is alkyltrialkylsilyl, said alkyl groups of the trialkylsilyl groups being the same or different and containing from 1 to 20 carbon atoms. 
     
     
       7. The composition of matter of  claim 5  wherein said Group 13 element is boron or aluminum and said fluoroaryl ligands are perfluorophenyl. 
     
     
       8. The composition of matter of  7  claim wherein each of said fluoroaryl ligands are para-substituted with said siloxy group replacing the para-fluorine atom. 
     
     
       9. A composition of matter represented by the formula: 
       
         
           [Ct] + [M(ArF) n ((ArF)OSiR 3 ) 4−n ] − ,  
         
       
       where [Ct] +  is cation capable of abstracting an alkyl group, or breaking a carbon-metal bond, of organometallic compounds containing such, M is boron or aluminum, ArF is a fluorinated aryl group, each R is a C 1 -C 30  hydrocarbyl or hydrocarbylsilyl substituent, and n is 0-3. 
     
     
       10. The composition of  claim 9  wherein ArF is a perfluorinated aryl group wherein said aryl group is selected from the group consisting of phenyl, biphenyl, and napthyl . 
     
     
       11. The composition of  claim 10  wherein each R independently is a C 1 -C 20  a linear, branched or cyclic aliphatic hydrocarbyl or hydrocarbylsilyl substituent. 
     
     
       12. The composition of  claim 11  wherein each R is attached to Si by a secondary or tertiary carbon atom. 
     
     
       13. The composition according to  claim 11  where [Ct] +  is selected from the group consisting of anilinium and ammonium cations, trityl carbenium cations, Group 11 metal cations, silylium cations, the cations of the hydrated salts of Group 1 or 2 metals, and derivatives of the foregoing anilinium, ammonium, trityl carbenium, and silylium cations containing C 1 -C 20  hydrocarbyl, hydrocarbylsilyl, or hydrocarbylamine substituents for one or more hydrogen atoms of said cations. 
     
     
       14. A composition of matter represented by the formula: 
       
         
           [Ct] + [M(ArF) n ((ArF)OSiR 3 ) 4−n ] − ,  
         
       
       where [Ct] +  is an anilinium and ammonium cation, ArF is a fluorinated aryl group selected from the group consisting of phenyl, biphenyl and napthyl, each R is a C 1 -C 20  hydrocarbyl substituent attached to the Si atom through a secondary carbon atom, and n is 0-3. 
     
     
       15. The composition of  claim 14  wherein n=0 and each R is isopropyl.